Stain resistant composition containing sulphonated surfactant

ABSTRACT

A direct application process by spray, pad, foam, flood or roller coating of a chemical composition of Novolak resin, polymethacrylic acid, sulphated or sulphonated surfactants and a fluorochemical to provide stain resistance/release to fibrous material, particularly nylon and wool carpets. The finish offers desirable oil, water and dry soil repellency and acid dye stain release without adverse effect on texture (handle) and pile opening. The invention relates to the use of diethanolamine lauryl sulfate as a foaming surfactant that also has stain release property against artificial coloring material commonly found in food and beverages.

FIELD OF THE INVENTION

This invention relates to a composition and process for providing stainrelease/resistance to fibrous materials, particularly polyamide fibrousmaterials such as nylon and wool carpets, nylon, wool, silk fabrics andnatural and synthetic leathers. The invention also relates to a directapplication process for providing stain release/resistance to fibrousmaterials.

BACKGROUND

Fibrous polyamide articles such as nylon and wool carpets, nylon, wooland silk fabrics, natural leather and synthetic fibers are particularlysusceptible to staining by natural and artificial acid colorants such asare commonly found in many foods and beverages. There has been a longfelt need for compositions and processes for economically providing suchfibrous polyamide articles with resistance to acid colorant staining.

U.S. Pat. No. 4,081,383 (Warburton, Jr., et al.) discloses ananti-soiling treatment for carpets and carpet yarns. The carpet orcarpet yarns prior to carpet manufacture are coated with a polymericmaterial containing either (A) a blend of a methacrylic acid emulsioncopolymer having an epoxy resin, or (B) a methacrylic acid emulsioncopolymer having epoxy monomer units therein. The copolymer in eithercase contains 40% to 70% by weight methacrylic acid.

U.S. Pat. No. 4,669,812 (Munk et al.) discloses a method for impartingstain resistance to fibers containing free amino groups, and especiallypolyamide fibers by contacting the fiber with a solution of an aliphaticsulphonic acid containing 8 to 24 carbons, under acidic conditions. Ifthe fibers are not thoroughly rinsed after application of the aliphaticsulphonic acid the product of this method after being dried has anundesirable finish due to the deposition of a filmy coating.

U.S. Pat. No. 4,579,762 (Ucci) discloses stain resistant nylon carpet inwhich the nylon fibers are made from polymers modified to contain, as anintegral part of its polymer chain, aromatic sulphonate units and inwhich the backing adhesive contains a fluorochemical.

U.S. Pat. No. 4,329,391 (McAlister) discloses the treatment of syntheticfibers with a sulphonated polyester stain-releasing finish in an aqueousbath which includes the addition of water soluble salts to the aqueousfabric treating bath.

U.S. Pat. No. 3,322,488 (Freeman) discloses sulphomethylatedcondensation products of bisphenols and aldehydes for use in treatingsynthetic polyamide and polyurethane fibers to render them resistant toacid and direct dyes.

Australian Patent No. 599427 discloses a method for imparting polyamidematerials with stain resistance to natural and synthetic colorants whichcomprises contacting the polyamide material with a water-solubledivalent metal salt of a partially sulphonated novolak resin.

Australian Patent No. 632641 (hereafter the "'641 patent") describes amethod for imparting stain resistance to fibrous polyamide materials inwhich the polyamide materials are coated with stain resistant agentscomprising (a) a partially sulphonated novolak resin, and (b)polymethacrylic acid, copolymers of methacrylic acid or combinations ofsaid polymethacrylic acid and copolymers of polymethacrylic acid, orcombinations of (a) and (b).

Conventional treatment processes require thorough washing of the treatedpolyamide material prior to drying in order to remove resin which is notassociated with the fibers. Unfixed reagents cause gluing of the fibers.In terms of processing or treating large amounts of material, this isinconvenient and costly, as well as environmentally problematic giventhe organic waste produced.

Thus, there currently exists a need for compositions and processes forimparting stain resistance to fibrous materials which do not adverselyeffect the finish of the treated fiber, which fully treat the fibrousmaterial avoiding "dead spaces", and which do not reduce the performanceof fluorochemical treatments for oil and water repellency.

DISCLOSURE OF INVENTION

According to a first aspect of the invention there is provided anaqueous treating composition for providing stain release properties tofibrous materials which comprises:

(a) polymethacrylic acid or copolymers of methacrylic acid orcombinations thereof;

(b) a partially sulphonated novolak resin;

(c) a surfactant containing a sulphate or sulphonate moiety; and

(d) water.

In a preferred embodiment, the sulphonated surfactant is an aromatic oraliphatic mono- or poly-sulphonated fatty acid. In a still furtherpreferred embodiment, the sulphonated surfactant is a sulphonated fattyacid alkanolamine condensate.

This invention is also directed to a process for providing fibrousmaterial and leather with stain release properties which comprisesapplying directly to said material a composition which comprises:

(a) polymethacrylic acid or copolymers of methacrylic acid orcombinations thereof;

(b) a partially sulphonated novolak resin;

(c) a surfactant containing a sulphate or sulphonate moiety; and

(d) water and thereafter drying the material.

In a further preferred embodiment the treatment composition is appliedto fibrous materials using a foaming agent as a carrier.

DETAILED DESCRIPTION

The aqueous treating composition for providing stain release propertiesto fibrous materials and leather comprises three key components:

(i) polymethacrylic acid or copolymers of methacrylic acid orcombinations thereof,

(ii) a partially sulphonated novolak resin, and

(iii) a surfactant containing a sulphate or sulphonate moiety.

Preferably, the treatment composition also includes a volatile organicacid.

When the composition of the invention is applied to fibrous material,particularly polyamide fibers, such as nylon and wool carpets, nylon,wool, silk fibers and fabrics, natural and synthetic leathers and thelike, stain release properties are imparted without loss of productfinish.

The term "stain release" used herein refers to the property of readyrelease of stains which have been absorbed by fibrous materials orleather. The term "stain resistance" used herein refers to anti-wettingproperties which result from treatment of fibrous materials or leatherwith fluorochemicals.

The polymethacrylic acid, copolymers of methacrylic acid, orcombinations thereof are embraced in this disclosure by the term"methacrylic polymer", which is intended to include polymethacrylic acidhomopolymer as well as polymers formed from methacrylic acid and one ormore other monomers.

The monomers useful for copolymerization with the methacrylic acid aremonomers having ethylenic unsaturation. Such monomers include, forexample, monocarboxylic acids, polycarboxylic acids, and anhydrides;substituted and unsubstituted esters and amides of carboxylic acids andanhydrides; nitriles; vinyl monomers; vinylidene monomers; monoolefinicand polyolefinic monomers; and heterocyclic monomers.

Representative monomers include, for example, acrylic acid, itaconicacid, citraconic acid, aconitic acid, maleic acid, maleic anhydride,fumaric acid, crotonic acid, cinnamic acid, oleic acid, palmitic acid,vinyl sulphonic acid, vinyl phosphoric acid, alkyl or cycloalkyl estersof the foregoing acids, the alkyl or cycloalkyl groups having 1 to 18carbon atoms such as, for example, ethyl, butyl, 2-ethylhexyl,octadecyl, 2-sulphoethyl, acetoxyethyl, cyanoethyl, hydroxyethyl andhydroxypropyl acrylates and methacrylates, and amides of the foregoingacids, such as, for example, acrylamide, methacrylamide,methylolacrylamide, and 1,1-dimethylsulphoethylacrylamide,acrylonitrile, methacrylonitrile, styrene, α-methylstyrene,p-hydroxystyrene, chlorostyrene, sulphostyrene, vinyl alcohol, N-vinylpyrrolidone, vinyl acetate, vinyl chloride, vinyl ethers, vinylsulphides, vinyl toluene, butadiene, isoprene, chloroprene, ethylene,isobutylene, vinylidene chloride, sulphated castor oil, sulphated spermoil, sulphated soybean oil, and sulphonated dehydrated castor oil.Particularly useful monomers include, for example, ethyl acrylate,itaconic acid, sodium sulphostyrene, and sulphated castor oil. Mixturesof the monomers can be copolymerized with the methacrylic acid.

The methacrylic polymers useful in the present invention can be preparedusing methods well known in the art for polymerization of ethylenicallyunsaturated monomers.

Preferably, the methacrylic acid comprises about 30% to 100% by weight,more preferably 60% to 90% by weight, of the methacrylic polymer. Theoptimum proportion of methacrylic acid in the polymer is dependent onthe comonomers used, the molecular weight of the copolymer, and the pHat which the material is applied. When water-insoluble comonomers, suchas ethyl acrylate, are copolymerized with the methacrylic acid, they maycomprise up to about 40% by weight of the methacrylic polymers. Whenwater-soluble monomers, such as acrylic acid or sulphoethyl acrylate arecopolymerized with the methacrylic acid, the water-soluble comonomerspreferably comprise no more than 30% by weight of the methacrylicpolymer and preferably the methacrylic polymer also comprises up toabout 50% by weight water-insoluble monomer.

Generally, the methacrylic polymer should be sufficiently water-solublethat uniform application and penetration of the polymer into the fibersurface can be achieved.

The glass transition temperature of the methacrylic acid copolymer canbe as low as about 35° C. although high glass transition temperaturesare preferred. When polymers having high glass transition temperatures,that is, as high as 230° C. or higher, are used, an additional benefitof improved soil resistance of the fibrous polyamide substrate can beobtained.

The weight average molecular weight and the number average molecularweight of the methacrylic polymer should be such that satisfactory stainresistance is provided by the polymer. Generally, the higher 90% byweight of the polymer material preferably has a weight average molecularweight in the range of about 3000 to 100,000. Generally, the lower 90%by weight of the polymer material preferably has a number averagemolecular weight in the range of about 500 to 20,000 more preferably inthe range of about 800 to 10,000. Generally, more water-solublecomonomers are preferred when the molecular weight of the polymer ishigh and less water-soluble or water-insoluble comonomers are preferredwhen the molecular weight of the polymer is low.

Commercially available methacrylic polymers generally useful in thepresent invention include Leukotan™ 970, Leukotan™ 1027, Leukotan™ 1028and Leukotan™ QR 1083 available from Rohm and Haas Company.

The partially sulphonated novolak resins useful in this inventioninclude known substances such as those compositions which arecondensation products of formaldehyde with bis (hydroxyphenyl) sulphoneand phenylsulphonic acid. Instead of, or in addition to, formaldehyde,another aldehyde such as, for example, acetaldehyde, furfuraldehyde, orbenzaldehyde, can be used to make the condensation product. Also, otherphenolic compounds such as, for example, bis(hydroxyphenyl)alkane, forexample, 2,2-bis(hydroxyphenyl)propane, and bis(hydroxyphenyl)ethercompounds can be used instead of, or in addition to, thebis(hydroxyphenyl)sulphone. The sulphonated novolak resin is partiallysulphonated, that is, has a sulphonic acid equivalent weight of about300 to 1200, preferably 400 to 900.

Examples of such resins are disclosed in U.S. Pat. No. 4,592,490 (Blythet al.). Also commercially available sulphonated novolak products areavailable such as: FX-369, a stain release product available fromMinnesota Mining and Manufacturing Company, St. Paul, Minn., U.S.A.;Intratex™ N available from Crompton and Knowles Corp., North Carolina,U.S.A.; Erional™ PA available from Ciba-Geigy AG, Basle, Switzerland;Nylofixan™ P available from Sandoz

Chemicals Ltd., North Carolina, U.S.A.; Mesitol™ NBS available fromMobay Chemical Corp., Pennsylvania, U.S.A.; Resist 4™ available fromLyndal Chemical Co., U.S.A.; Mak™ 7 available from Allied Signal Inc.,New Jersey, U.S.A.; NRD 329 and NRD 332 available from DuPont Co.,Delaware, U.S.A.; Ameriolate™ available from American Emulsions Co.Inc., Georgia, U.S.A.; and Synthabond™ 1938 available from PiedmontChemical Industries, North Carolina, U.S.A. Sulphonation of phenoliccompounds is taught, for example, in Sulfonation and Related Reactions,E E Gilbert, Interscience Publishers, 1965. Condensation ofphenol-formaldehyde resins is taught, for example, in Phenolic Resins, AKnopf et al., Springer-Verlag, 1985.

Other partially sulphonated novolak resins which may be used in place ofor in addition to the aforementioned novolak resins include those resinsdescribed in Australian Patent No. 599427, that is, a water-solubledivalent metal salt of a partially sulphonated novolak resin, whereinthe salt contains less than 1% sulphonic acid moieties. The teachings ofAustralian Patent No. 599427 are incorporated herein by reference intheir entirety.

The sulphated or sulphonated surfactant used in preparing the aqueoustreating compositions of this invention include alkyl aryl sulphonatedand hydroxyethylated fatty amines and their derivatives, such asUnivadine™ PS-AU available from Ciba-Geigy AG, Basle, Switzerland, whichcomprises an alkyl aryl sulphonate and hydroxyethylated fatty amine ofthe formulae: ##STR1## in which R is an alkyl chain of 14 to 18 carbons,and Miltopan™ D503 available from Henkel Australia Pty. Ltd., Victoria,Australia which has the formula: ##STR2## in which Y is an alkali, andR₁ is a C6 to C18 group which substitutes the phenyl ring at the 1, 2 or3 position; sodium alkyl diphenyl ether disulphonates, such as Pelex™SS-L available from Kao Corporation; sodium dodecyl diphenyl oxidedisulphonate with high sulphur bond (containing ammonium thiosulphate)such as Pelex™ SS-H; dodecyl (sulphophenoxy) benzene sulphonic acid,disodium salt; oxybis (dodecylbenzene sulphonic acid) disodium salt suchas Rhodacaltm DSB, Siponate™ DSB available from Rhone-Poulenc Pty. Ltd.,Victoria, Australia; oxybis (dodecylbenzene sulphonic acid) disodiumsalt containing xylene, Kemmat™ SN18 available from Harcros ChemicalsPty. Ltd., New South Wales, Australia; aryl sulphonates; fatty aminepolyglycol ether (sulphonate ethylene oxide condensate) such as TEBAN™ES available from Dr TH Bohme Chemie, Geretsried, Germany; sodium saltsof highly sulphonated oil/ethylene oxide condensate, such as MATEXIL™LA-NS available from ICI, New South Wales, Australia; dodecyl(sulphophenoxy) benzene sulphonic acid, disodium salt oxybis(dodecylbenzene sulphonic acid) disodium salts containing at least 1%sodium sulphate and at least 3% sodium chloride, such as Dowfax™ 2-A1available from Dow Chemicals Pty. Ltd., New South Wales, Australia;benzene sulphonic acid, dodecyl (sulphophenoxy) disodium salt,monosodium and didodecyl disulphonated diphenyl oxide such as CALFAX™DB-45 available from Pilot Chemicals Inc., Los Angeles, Calif., U.S.A..Other examples of sulphonated surfactants which may be used in theinvention are disclosed in McCutcheon's Emulsifiers and Detergents,International Edition, 1983.

Aromatic or aliphatic mono or poly-sulphonated fatty acids arepreferred, such as those containing 8 to 20 and more preferably 8 to 16carbon atoms in the fatty acid aliphatic chains. Examples of alkylgroups which may used in the sulphonated fatty acids include, octyl,nonyl, decyl, dodecyl (lauryl), eicosyl, nicosyl, docosyl, tricosyl andtetracosyl group. The alkanoyl groups which may be used aremonounsaturated analogues of those above, that is, octenyl, nonenyl andthe like.

Alkanolamine and alkanolamide sulphonated fatty acids are preferred suchas those containing C₁ to C₁₀ alkyl groups. These compounds are thecondensation products of aliphatic fatty acids and hydroxy alkyl amines.Reference to alkanolamine and alkanolamide sulphonate fatty acidsincludes the mono-, di- and tri-alkanolamine and alkanolamidecondensates. Fatty acid diethanolamide and diethanolamines are versatileand widely used surfactants. Examples of the fatty acid component ofsuch compounds include ricinoleic, lauric, linoleic, tall oil, coco,lauric, oleic, stearic, capric and isosteric acid, all of which aredescribed in Kirk-Othmer Encyclopedia of Chemical Technology 3rdEdition, Volume 22, at Table 24, which reference is incorporated hereinin its entirety.

The most preferred sulphonated fatty acids according to this inventionare the ethanolamine lauryl sulphates, particularly diethanolaminelauryl sulphate, a commercially available surfactant which is sold underthe trade mark Empicol DA by Albright & Wilson, Victoria, Australia.Diethanolamine lauryl sulphate has the following formula:

    C.sub.11 H.sub.23 OSO.sub.3.NH.sub.2 (CH.sub.2 CH.sub.2 OH).sub.2

The fatty acid ethanolamine lauryl sulphates, as well the othersulphonated fatty acid surfactants, can be applied in the form of a foamgiven their detergent properties. This is an advantage, as will behereinafter described in further detail.

The respective amounts of the methacrylate, novolak resin andsulphonated surfactant used in the compositions of the invention arethose which provide the desired degree of stain release from the fibrousmaterials, without adversely effecting the finish of the fibrousmaterials or reducing the effects of fluorochemical treatments for waterrepellency. It has surprisingly been found that sulphonated surfactantscan replace to a significant extent the methacrylate polymer and novolakresin previously thought to be necessary in significant quantity.

This substitution enhances the effects of the treating composition in anumber of unexpected ways. Firstly, the substitution provides a greaterpenetration into the fibrous materials, thereby ensuring that thetotality of fibers are treated. Secondly, the gluing effect whichresults from the direct application of high concentrations ofmethacrylate polymer in the order of 15% to 90% in association with anovolak resin is avoided giving a soft handling finish to polyamidefibers. This is particularly significant in the carpet industry where ahigh texture bloom (opening of the yarn ends to give softer feel orhand) is demanded by carpet customers, particularly in respect of nyloncarpets. As treated fibers according to this invention are not washed toremove non-fixed material, significant economic and environmentalbenefits apply. Thirdly, methacrylate polymers and novolak resins reducethe effects of fluorochemical treatment due to their strong hydrophilicproperties and hence the ability to reduce the amounts of thesematerials without diminishing stain release properties is an importantadvantage.

Generally, the compositions of the invention contain from 10% to 90% byweight of sulphonated surfactant, preferably 30% to 80% by weight andmore preferably 30% to 60% by weight. The methacrylate polymer andnovolak resin are generally provided in approximately the same weightpercentage in the composition, in amounts from about 5% by weight to 30%by weight, preferably 10% to 20% by weight.

The treating compositions according to the invention may contain otheringredients which increase effectiveness, stability of the composition,miscibility, foaming properties and the like. For example, thesecompositions may contain ingredients which make the composition moresuitable for use and less susceptible to degradation.

Minor amounts of additives such as wetting agents improve migration ofcompositions along fiber tips and improve stability of the compositions.An example of such a wetting agent is wetting agent NF™ from Hoechst AGwhich is a modified diestersulphosuccinate acid surfactant.

Minor amounts of de-aerating and stabilizing additives may be used in anamount from 1% to 10% by weight. An example of such an ingredient isLeonil™ GP-Z from Hoechst AG, which composition is anonylphenylethoxylate surfactant.

Divalent metal salts may be used in the treating compositions. Suitabledivalent metal salts include water-soluble inorganic and organic saltsof metals, such as magnesium, calcium and zinc. Organic metal saltsinclude, for example, acetates and formates of the aforementionedmetals. Preferred divalent metal salts are magnesium sulphate, magnesiumchloride and calcium chloride. Mixtures of two or more divalent metalsalts may be used. When divalent metal salts are added to the treatingcomposition, they are preferably used in an amount of at least 0.5% byweight of solids, based on the weight of the fabric ("owf"), morepreferably at least 1% by weight of solid owf, most preferably at least2% by weight of solid owf.

Preferably, an organic acid, more preferably a volatile aliphaticcarboxylic acid, is used in the treatment compositions according to theinvention. Examples of volatile carboxylic acids include formic acid,acetic acid, propionic acid, butyric acid and valeric acid, with formicacid and acetic acid being particularly preferred. Acids are believed toassist in fixation of stain release reagents to polyamide fibers.Conventional methods in the art use strong mineral acids andnon-volatile acids for fixation of novolak resins and methacrylatepolymers. These acids must be removed by washing of the fibers. Volatileacids, in contrast, are simply removed from polyamide fibers duringconventional drying procedures, which for carpets is above 120° C. Undersuch conditions, volatile acids are liberated from the fibers leaving noacidic residue. Acids may be used in an amount from 0.1% to 5% by weightof the composition at a pH of about 2.0 to 4.0. Without wishing to belimited to any reaction mechanisms, it is believed that at low pH theaffinity of the stain release reagents and the polyamide fiber isgreater, allowing chemical bonding by dipolar attraction as well ascovalent bonding to amine groups on the fiber (the sites of dyebinding).

Foaming agents as are well known in the art may be incorporated into thecomposition of the invention in order to assist application as a foam.Alternatively, the composition itself may form a foam on agitation dueto the properties of the sulphonated surfactant or other components.

The aforementioned ingredients may be simply added to the composition ofthe invention prior to treating fibrous material.

The composition of the invention may be coapplied with a fluorochemicalcomposition in order to provide oil, water and soil repellency (that is,stain resistance) in addition to stain release properties. Thefluorochemical composition is added in an appropriate amount to thetreating solution. The resultant compositions may be referred to asstain release/resistant compositions.

The fluorochemicals which may be used in the present invention forproviding oil and water repellency include anionic, cationic, ornonionic fluorochemicals which are usually provided as aqueousemulsions, such as the fluorochemical allophanates disclosed in U.S.Pat. No. 4,606,737 (Stern); fluorochemical polyacrylates disclosed inU.S. Pat. Nos. 3,574,791 (Sherman et al.) and 4,147,851 (Raynolds);fluorochemicals urethanes disclosed in U.S. Pat. No. 3,398,182(Guenthner et al.); fluorochemical carbodiimides disclosed in U.S. Pat.No. 4,024,178 (Landucci); fluorochemical guanidines disclosed in U.S.Pat. No. 4,540,497 (Chang et al.); and fluorochemical potassium salts(which are self curing or cross-link under ambient temperatures).

The fluorochemical, when included in the treating solution, ispreferably present in an amount that is sufficient to retain on thefiber of the finished article about 200 to 1000 ppm fluorine based onthe weight of the fiber. This can generally be achieved by using atleast about 0.4% product owf, more preferably at least 0.7% product owf,most preferably 0.8% product owf. Generally, amounts of thefluorochemical in excess of 2% product do not appreciably improve theoil and water repellency.

The respective components of the treating composition are admixedutilizing standard procedures. Heat and agitation may be applied asnecessary. The pH of the treating solutions depends on the fiber beingtreated. Generally, the pH is acidic in the range of 2.0 to 4.0, morepreferably 2.5 to 4.5. pH may be adjusted with acid or base reagents.

The treatment composition according to the invention can be convenientlyapplied directly to a fibrous substrate by spraying, dipping, coating,padding, foaming or roller coating application, or by a combination oftwo or more of these methods. Application by way of foaming isparticularly preferred as the amount of composition applied is muchdecreased compared to other applications, wastage of treating solutionis minimized and processing is streamlined. In this regard, the use ofalkanolamine and alkanolamide sulphonated fatty acids are particularlypreferred given their detergent properties and the subsequent ease withwhich foaming preparations can be prepared according to processes wellknown in the art. As no washing is required to remove non-fixedreagents, overall processing is streamlined and waste productsminimized.

The interaction between the components of the treatment composition ofthe invention may be regarded as synergistic. Alternatively, the resultof the combination may be regarded as unexpected. These considerationsarise from a number of perspectives. Sulphonated surfactants have nothitherto been proposed as stain release agents. When applied directly tofibrous materials such as carpets at high levels, excess sulphonatedsurfactants have the disadvantage that they leave a filmy residue afterdrying and actually attract dry soil, (such problems are associated withthe processes of U.S. Pat. No. 4,699,812 (Munk et al.) described earlierin this document). However, when sulphonated surfactants are used incombination with a methacrylate polymer and novolak resin (that is, tosubstitute a proportion of these components), these problems areovercome, particularly in the situation where the sulphonated surfactantis used to an appreciable extent, such as 15% to 80% by weight of thetreatment composition.

The use of a sulphonated surfactant in the treatment composition of theinvention does not adversely effect the actions of the methacrylatepolymer and novolak resin and removes disadvantages associated withthese agents. For example, methacrylate polymers when applied directly(that is, without washing after application) to fibrous materials maycause aggregation or a gluing effect which adversely effects thefinished product, giving a hard texture due to the aggregated fibers aswell as a poor texture bloom. This is a particular problem in nyloncarpets where the weight of the carpet determines costs. Where standardnylon carpets are treated with methacrylate polymers and novolak resinby direct application, the fiber aggregation is such that the carpetappears to have a much less open bloom and therefore gives theimpression of being of a much lesser quality, that is, less weight persquare yard. Utilizing the compositions of this invention, however,carpets are provided with a normal open bloom which gives the impressionof a much greater weight carpet, particularly with carpet yarn densitybelow 20 oz/yd² (ounces/square yard).

The interaction between the components of the treatment composition ofthis invention also removes the problems associated with coapplicationof fluorochemicals for water and oil repellency. Methacrylate polymersand novolak resins have been found to be hydrophilic in nature and theuse of these treating compositions as in prior known proposals largelyreduces the effects of fluorochemical treatment, namely waterrepellency. In the treatment compositions of this invention theseproblems are overcome with the result that the methacrylate polymer andnovolak resin employed in the composition do not effect the performanceof coapplied fluorochemicals. This is particularly advantageous.

Fibrous material which may be treated according to this inventioninclude polyamide fibrous materials such as nylon and wool carpets,nylon, wool, silk fabrics and natural and synthetic leathers.

The following non-limiting examples serve to illustrate the invention.All ratios are by weight and percentages are weight percent unlessotherwise indicated.

TEST METHODS

A. Oil Repellency Test (OR)

The oil repellency of treated carpet and textile samples is measured bythe American Association of Textile Chemists and Colorists (AATCC)Standard Test Method No. 118-1983, which test is based on the resistanceof treated fabric to penetration by oils of varying surface tensions.Treated fabrics resistant only to Kaydol™, a brand of mineral oil andthe least penetrating of the test oils, are given a rating of 1, whereastreated fabrics resistant to heptane (the most penetrating of the testoils) are given a value of 8. Other immediate values are determined byuse of other pure oils or mixtures of oils, as shown in the followingtable:

    ______________________________________                                        STANDARD TEST LIQUIDS                                                         AATCC Oil Repellency Rating                                                   Number            Composition                                                 ______________________________________                                        1                 Kaydol ™                                                 2                 63:35 Kaydol ™: hexadecane by                                              volume at 21° C.                                     3                 n-hexadecane                                                4                 n-tetradecane                                               5                 n-dodecane                                                  6                 n-decane                                                    7                 n-octane                                                    8                 n-heptane                                                   ______________________________________                                    

The rated oil repellency corresponds to the most penetrating oil (ormixture of oils) which does not penetrate or wet the fabric after tenseconds contact. Higher numbers indicate better oil repellency.

In the test procedure the test sample is placed on a flat surface. Adropper pipette is used to gently place five drops of the selected oilonto the sample at 5 cm intervals. After ten seconds, if four out offive drops are still visible, the sample passes the test. A rating of"2" is generally considered a minimum requirement.

B. Water Repellency Test (WR)

The aqueous stain or water repellency of treated samples is measuredusing a water/isopropyl alcohol test, and the result is expressed interms of a water repellency rating of the treated fabric. Treatedfabrics which are resistant to a 100% water/0% isopropyl alcohol mixture(the least penetrating of the test mixtures) are given a rating of W;resistance to a 90% water/10% isopropyl alcohol mixture is given arating of 1, whereas treated fabrics resistant to 0% water/100%isopropyl alcohol mixture (the most penetrating of the test mixtures)are given a rating of 10. Other intermediate values are determined byuse of other water/isopropyl alcohol mixtures, in which the percentageamounts of water and isopropyl alcohol are each multiples of ten.Results are reported as an average of replicate testing. The waterrepellency rating corresponds to the most penetrating mixture which doesnot penetrate or wet the fabric after ten seconds.

The procedure involves placing five small drops of water/alcohol mixtureonto the carpet face. After ten seconds, if four out of five drops arestill visible, the sample passes the test.

A rating of "1" (90/10 water/isopropanol mixture) is generallyconsidered as a minimum requirement.

C. Dry Soil Repellency (DS)

This test is intended to measure the tendency of a carpet to resist drysoil during the use. The soil contains clay, carbon black, silica andmineral oil. It is deposited on to the carpet via a soil capsule in atumbler containing seventy steel balls. The tumbler rotates for tenminutes and the carpet samples are removed and the excess soil is blownoff by an air nozzle at 50 psi. The degree of soiling resistance ismeasured by comparing the soiled area to a standard rating board. A 5.0rating is the absolute standard of soil repellency and 3.0 is anacceptable soiling degree.

D. Twenty Four Hour Stain Release Test (SR)

This test is designed to evaluate the effectiveness of stain resistanttreatments on carpet against acid staining medium (artificial colouringsin food and drink). A stock solution using 80 mg of FD8C Red 40 isdissolved in one liter of water containing citric acid to pH 3.0±0.2; a15 ml aliquot of the staining medium is deposited on carpet sample via abottomless staining ring of approximately 50 mm internal diameter. Thestained sample was left untouched for 24±four hours in room temperature,on a flat and non-absorbing surface. It is rinsed in luke-warm runningwater until no more stain is released, then dried and rated against 3MStain Release Rating Scale--where a score of 8.0 is absolute stainrelease, 6.0 is average and scores under 5.0 are not acceptable.

E. MBTF Light Fastness (LF)

This test determines the colour fastness of textiles to light, using anartificial light source. A test specimen of the textile, together withblue light fastness standards, is exposed to the light from a 500 Wmercury vapour, tungsten filament lamp. Fading/colour change is ratedagainst the blue scale standards--while 8.0 as an absolute rating and5.0 as a minimum industry requirement.

F. Handle of Texture (HAND)

Assessment is done by subjectively "feeling" the surface texture andcomparing the sample to that from a conventional finish. The softnessdegree of the sample finished by foam co-application must be about thesame as the conventional finish which is described as the oneaccomplished by the hot flood of the stain release and spraying of theScotchgard™ product.

G. Opening of Texture (Bloom)

Assessment is done by visual or microscopic close-up observation of thetexture for the opening of the individual yarn (made up of a group offilament). An "open" bloom is defined as similar to that of the textureof carpet receiving no protective chemical finish, that is, thefilaments do not bundle closely together. This achievement isparticularly significant for lower weight carpets (below about 20 oz=680gsm). A carpet with an open bloom has the appearance of an expansion orspread of the carpet fibers, giving a greater apparent bulk. For a givenweight carpet, it is advantageous to provide the appearance of increasedbulk.

EXAMPLE 1

The stain release and other test properties outlined above were comparedusing sulphonated surfactants only, a combination of novolak resin andpolymethacrylate polymer, and the combination of sulphonated surfactant,novolak resin and polymethacrylate polymer according to this invention.

In this example, 108 grams of each product were dissolved in one literof water. The solution was applied to a 19 oz/yd² cut pile nylon 6,6carpet in an amount of 15% by weight of the carpet resulting in aminimum application level of 1.6% product on carpet (POC). The solutionalso contained 4 g of magnesium sulphate dihydrate and 47 g of ananionic fluorochemical (0.7% POC) in order to test for water and oilresistance, and soil repellency. The treatment compositions were appliedby direct spray, foam and pad methods. For the test results described inthis example, spray application was used. After application, the carpetwas subjected to drying in an oven at between 120° C. to 130° C. untildry. The parameters assessed were oil repellency (OR), water repellency(WR), dry soil repellency (DS), twenty four hour stain release (SR),MBTF of light fastness (LF), handle of texture (HAND) and opening oftexture (Bloom). The treatment composition of the invention containedthe following components:

    ______________________________________                                        1. methacrylate polymer                                                                         F-7867    15%                                               2. novolak resin  FX-369    14%                                               3. sulphonated surfactant                                                                       Empicol DA                                                                              50%                                               4. wetting agent  NF        1%                                                5. de-aerator     Leonil GP-Z                                                                             7%                                                6. formic acid              3%                                                7. water                    10%                                               ______________________________________                                    

The treatment composition was applied at 1.6% product owf.

Components (1) and (2) are commercially available products of MinnesotaMining and Manufacturing Company, St. Paul, Minn., U.S.A. Component (1)is a polymethacrylic acid polymer formed from methacrylic acid and oneor more monomers having ethylenic unsaturation. The molecular weight ofthe polymer is preferably in the range of 800 to 10,000 daltons. Thepartially sulphonated novolak resin (2) has a sulphonic equivalentweight of preferably 400 to 900.

Component (3) is from Albright & Wilson Australia Ltd., St. Marys, NewSouth Wales, Australia, and comprises diethanolamine lauryl sulphate.Component (4) is a non-flammable (NF) wetting agent from Hoechst AG,Frankfurt, Germany which comprises a modified diester sulphosuccinicacid surfactant, which component improves stability of the compositionat low temperature (below 5° C.). Component (5) is from Hoechst AG andcomprises a nonyl phenol ethoxylate and alkane sulphonate surfactants inisopropanol, and is used as a de-aerator as well as to assist insolubilization and stabilization of F-7867 and FX-369.

The test results obtained from the above treatments are set forth inTable 1 below:

    ______________________________________                                                OR  WR     DS     SR  LF  HAND   BLOOM                                ______________________________________                                        Surfactant/FC                                                                           4     3      2    6   6   Soft Filmy                                                                           Open                               Novolak/FC                                                                              4     1      3    7   2   Moderate                                                                             Partial                                                                       gluing                             Methacrylate/FC                                                                         4     0-1    4    7   6   Harsh  Gluing                             Novolak/metha-                                                                          4     0-1    4    8   6   Harsh  Gluing                             crylate/FC                                                                    Combination                                                                             4     3      3.5  8   6   Soft   Open                               ______________________________________                                    

These results clearly show the unsatisfactory results obtained with theapplication of surfactant, novolak resin, methacrylate polymer, and thecombination of methacrylate polymer and novolak resin when using thedirect application method.

The application of surfactant alone at an elevated level gave a poor drysoil repellency, that is, it has a soil attraction defect due toresidual surfactant left on the carpet. The use of surfactant alone inthe treatment of fibrous materials is unsatisfactory.

Treatment of the carpet sample with the methacrylate polymer gavesimilar results to that of the novolak resin. A significant gluing ofthe fibers occurred with a resultant hard texture. The water resistanceof the fluorochemical treatment was adversely affected.

In distinct contrast to the comparative treatments, the combinationaccording to the invention of methacrylate polymer, novolak resin andsulphonated surfactant gave a treated product with excellent properties.Particularly notable is the open bloom of the treated material, softtexture, excellent stain release properties and no effect on the oil andwater repellency of the fluorochemical treatment. The treatmentcomposition showed excellent penetration into the carpet pile.

When surfactant was present in an amount from 5% to 90%, excellent stainrelease properties were observed. When the combined amount of novolakresin and polymethacrylate exceeds about 40% by weight, the test productshows poor water repellency and handle texture. Such an effect was notobserved, however, in the presence of a sulphonated surfactant where thenovolak resin and methacrylate polymer were used in amounts up to about40% by weight.

In a specific group of tests the amounts of surfactant, novolak resinand polymethacrylic acid evaluated in the composition were as follows:

    ______________________________________                                        Surfactant            0% to 100%                                              Novolak resin         0% to 17%                                               Polymethacrylic acid: 0% to 88%                                               ______________________________________                                    

EXAMPLE 2

A series of sulphonated surfactants were tested in place ofdiethanolamine lauryl sulphate utilizing the test methods and proceduresof Example 1. Examples of surfactants investigated and the resultsobtained are set forth below:

(1) UNIVADINE PS-AU

Supplier: Ciba-Geigy Australia Pty. Ltd., Thomastown, Victoria,Australia

Composition: alkyl aryl sulphonated and hydroxyethylated fatty amine

Use of this product gave acceptable performance in the treatmentcomposition of the invention

(2) LANKROPOL WN

Supplier: Lankro Chemicals Ltd., Manchester, United Kingdom

Composition: alkylated diphenyl oxide disulphonates, sulphated monoesterof fatty acid, containing sodium salt.

Use of this product gave an acceptable result in the treatmentcomposition of the invention.

(3) TEBAN ES

Supplier: Dr TH Bohme Chemie GmbH & Co. Geretsried, Germany

Composition: Aryl sulphonates, fatty amine polyglycol ether (sulphonateethylene oxide condensate).

This composition gave treatment compositions at the lower end ofeffectiveness. The product showed some propensity to attract soil andgave a barely acceptable texture bloom after treatment.

(4) MILTOPAN D 503 PASTE/LIQUID

Supplier: Henkel Australia Pty. Ltd., Broadmeadows, Victoria, Australia

Composition: Neutralized alkyl lauryl sulphonate. CAS No. 7732-18-5

This compound produced a very satisfactory treatment compound whencombined with the novolak resin and methacrylate polymer. Minor problemswere noticed with texture bloom.

(5) KEMMAT SN 18

Supplier: Swift Watts Winter Pty. Ltd., Silverwater, New South Wales,Australia

Composition: Dimethyl benzene sulphonic acid, sodium salt, containingxylene (generally called sodium xylene sulphonate)

Resulting treatment composition was at the lower end of effectiveness,particularly in relation to stain release property.

EXAMPLE 3 Treatment by Direct Foam Application Followed by aDrying/Curing Step

Nylon 6,6 carpet was treated on a commercial scale using the combinationof the invention particularized in Example 1, namely containing 50%sulphonated surfactant, 14% methacrylate polymer and 15% sulphonatednovolak resin.

The product was applied by foam via a Texicon Autofoamer with a 1 mmapplicator slot. The composition of the invention was dosed at 1.6%product on carpet in conjunction with an anionic aliphaticfluorochemical at 0.7%. The following parameters were recorded:

    ______________________________________                                        Stain release composition:                                                                    108 g/L                                                       Fluorochemical: 47 g/L                                                        Magnesium sulphate dihydrate:                                                                 4 g/L                                                         Wet pick-up:    15% add-on based on dry carpet weight                         Blow ratio:     60:1                                                          Gap setting:    1                                                             Liquor back pressure:                                                                         45 psi                                                        Foam back pressure:                                                                           50 psi                                                        Foam quality:   continuous fine lather                                        ______________________________________                                    

The application was on wet carpet after dyeing and steam washing. Thecarpet was dried at 130° C. and was later latex backed. Performanceachieved was as follows:

    ______________________________________                                                  OR  WR     DS    SR  LF  HAND  BLOOM                                ______________________________________                                        Sample      4     3      3.5 8   6   Soft  Open                               Desirable performance                                                                     2     1      3.0 7   5   Soft  Open                               ______________________________________                                    

Large scale carpet treatment using coapplication of the treatmentcomposition and the fluorochemical in the form of a foam followeddirectly by drying the carpet gave a product of excellent finish andperformance. The Handle and the texture is superior to conventionaltreatments applied directly (that is, without a post-treatment washingstep).

EXAMPLE 4 Treatment by Direct Spray Application Followed by AirDrying/Curing

This example indicates that the composition of the invention can beapplied in conjunction with a fluorochemical directly to installedcarpets to give similar properties of stain release and stain resistanceto carpets treated commercially during the manufacturing stage.

In this example, the compound and fluorochemical were applied via anairless sprayer at 25 psi pressure, 7 m/minute speed, at 15% wet add-onto a wet/precleaned nylon 6,6 carpet of 680 g (19 oz/yd²).

The solution contained the following ingredients per liter:

108 g (1.6% product on carpet) of the treatment composition of Example1.

100 g (1.5% product on carpet) of a fluorochemical potassium salt, whichcomprises a C6/C8 hybrid potassium salt of a fluoroaliphatic acid inbutyl cellosolve and isopropanol.

792 g water.

The carpet was allowed to air dry at ambient temperature at 23±2° C.overnight. Standard tests of stain release and stain resistance werecarried out with the following performance:

    ______________________________________                                                  OR  WR     DS    SR     HAND  BLOOM                                 ______________________________________                                        Sample      2     1 to 2 4.0 7.5 to 8.0                                                                           Soft  Open                                Desirable performance                                                                     2     1      3.0 7      Soft  Open                                ______________________________________                                    

The composition of the invention is therefore also suitable forapplication to installed carpet and other polyamide fabrics. Heattreatment is unnecessary when fluorochemicals which self-cure orcross-link under ambient conditions are used.

I claim:
 1. An aqueous treating composition for providing stain releaseproperties to fibrous materials which comprises:(a) an acrylic polymerselected from the group consisting of: polymethacrylic acid, copolymersof methacrylic acid, and combinations thereof, (b) a partiallysulphonated novolak resin, (c) a surfactant comprising a mono-, di- ortri-ethanolamine lauryl sulphate, and (d) water.
 2. The composition ofclaim 1 which comprises:(a) 5% to 30% by weight of a methacrylatepolymer, (b) 5% to 30% by weight of a partially sulphonated novolakresin, and (c) 10% to 90% by weight of a surfactant comprising a mono-,di- or tri-ethanolamine lauryl sulphate.
 3. The composition of claim 1which additionally includes a fluorochemical for providing oil and waterrepellency.
 4. The composition of claim 1 which additionally includes avolatile organic acid, which can be removed after application of thecomposition to a substrate by drying at temperatures above 120°.
 5. Aprocess for providing a substrate material selected from fibrousmaterial and leather with stain release which comprises applying to saidmaterial a composition according to claim 1 and thereafter drying thematerial.
 6. A process according to claim 5 wherein the fibrous materialis a carpet, textile fabric or synthetic leather.
 7. A process accordingto claim 5 wherein a fluorochemical is coapplied or applied separatelyto the composition according to claim 1 in order to provide oil andwater repellency.
 8. A process according to claim 7 wherein drying ofthe treated material takes place under ambient conditions in thepresence of a fluorochemical which self cures or cross-links underambient conditions.